洗涤剂助剂的演变——从磷酸盐到沸石到硅酸盐

在洗涤剂组分中，三聚磷酸钠、A型沸石和层状结晶二硅酸盐SKS－6已是被广泛接受的助剂。新型洗涤剂的开发促进了新型洗涤助剂的应用。针对这些助剂进行了产品的市场趋势、生态效应和产品应用等方面的比较。     

Organic acids as builders in linear alkylbenzene sulfonate detergent formulations

Sodium salts of citric, glycolic, diglycolic and three sugar acids, directly derived from D-glucose, were evaluated as builders in a formulation for a linear alkylbenzene sulfonate detergent. Only sodium citrate and diglycolate were at least 60% as effective as sodium tripolyphosphate in building action in hard water. Detergency appeared to be related to calcium sequestration by the salts at pH 10. No. Utillz. Res. Dev. Div., ARS, USDA.     

Recent studies on the roles of silicate builders in detergent formulations

In today’s detergency silicates are called upon to perform more roles than in the past. The providing of alkalinity and soil suspension properties remain important, but the less obvious properties of silicates are often unrecognized. Interaction between silicates and phosphates in solution lead to enhanced builder properties over each component alone. Additionally, silicate acts to slow down the reversion of high-molecular-weight phosphates. Silicate solutions may be used to hydrate sodium tripolyphosphate commercially in order to provide useful particles containing both builders in easily soluble form. The alkalinity of sodium silicate may be used to convert sodium trimetaphosphate to tripolyphosphate, again providing a particle with both builders present. Silicates prevent corrosion of metals, especially in the presence of phosphates. This corrosion prevention is discussed in regard to the effect of alkali-to-silica ratio and the influence of neutral salts on the system. The prevention of insoluble formation can be achieved by increasing the quantity of silicate in the formulation or by providing a vapor-barrier package. This paper also reviews the fundamental properties of sodium and potassium silicates that have importance from the standpoint of detergency.     

洗涤剂助剂的发展

介绍了三聚磷酸钠在洗涤剂中的应用和富营养化,洗涤剂助剂从三聚磷酸钠到4A沸石以及最新的层状硅酸钠的发展过程,讨论了洗涤剂配方的发展趋势和对环境的影响。     

Analytical test methods for the inorganic portion of the detergent products

Summary Evaluation of available methods for preliminary examination of the inorganic portion of detergent compositions indicates that this phase of the analysis has a relatively satisfactory status. Utilization of various spectrographic devices can prove most helpful in both preliminary and in final analysis of detergent components. Several integrated schemes of analysis are available. Most of them are as yet incomplete with respect to a good analysis of sodium tripolyphosphate, but recently described techniques hold considerable promise. These general schemes are under review with the objective of using in them more effective techniques for certain components. Individual component analyses are under critical examination, particularly those for the phosphates. A recently introduced chromatographic technique promises improvement here. Improved techniques for the determination of silica merit examination for integrated schemes as well as for single component analysis. Even sulfate analysis may be improved if published methods are indicative. Analyses for optical brighteners, corrosion inhibitors, and carboxymethyl cellulose are needed and do not now exist in satisfactory form.     

Determination of sodium carboxymethylcellulose in detergent products

Sodium carboxymethylcellulose in detergent products reacts with phenol in a sulfuric acid media to give a colored reaction product, the absorbance of which is measured at 490 mμ. No interference was experienced from the normal constituents of detergent products. The reproducibility was found to be±0.05% absolute.     

Natrium-Aluminium-Silicate - Eigenschaften und Anwendungen

Sodium Aluminium Silicates - Properties and Application Sodium aluminium silicates in amorphous and crystalline form are used since many years in various technical processes. The crystalline sodium aluminium silicates, e. g. zeolites, belong to the group of structured silicates and are known for their reversible water uptake and alkaline earth exchange properties. Recently, sodium aluminium silicates have gained considerable importance since their cation exchanging ability can be utilized in washing agents for the removal of undesirable hardness of water. Thus, the polyphosphates used in washing agents can possibly be substituted. Zeolites can be supplied to the detergent industry in the form of powder or suspension. Production of the powder by spray drying does not involve special problems. Incorporation of the powder into the slurry of the detergent appears to be an anachronism from the viewpoint of energy saving. Optimization work on suspensions of zeolite yielded stable products with 45 to 48% zeolite content. The theory of critical particle concentration was applied in this work.     

Assessing detergent safety: A comparison of a nonphosphate laundry detergent with phosphate detergents

The potential hazard of a carbonate-based, phosphate-free detergent was compared with that of a variety of granular and liquid phosphate detergents. Evaluations were made using methods prescribed by the Federal Hazardous Substances Act (FHSA) and others designed to more closely approximate exposure in actual use. Some phosphate products produced esophageal and gastric mucosal irritation similar to that produced by the nonphosphate detergent, while others caused varying, lesser degrees of injury. The nonphosphate detergent, as well as several phosphate products, was seriously irritating to the unwashed eye at required FHSA test levels. Under more realistic conditions, eye irritation was reduced significantly. Skin irritation by the nonphosphate product was comparable to that by phosphate detergents, and in some cases was lower. In skin irritation tests with human subjects, results with the carbonate detergent were equal to or lower than those obtained with phosphate detergents. The carbonate detergent was found not to be phototoxic, nor a contact- nor photo-sensitizer. Total alkalinity was shown not to correlate with the severity of tissue injury in either test animals or in man. Presented at the AOCS Short Course, “Update on Detergents and Raw Materials,” Lake Placid, New York, June 1971.     

Starch-derived polyelectrolytes as builders in heavy duty detergent formulations

A study was made of some carboxylated starches as builders in detergent formulations that contained linear alkylbenzene sulfonate. Two types of standard soiled cotton were used with water at 300 ppm hardness. Dicarboxyl starches and carboxymethyl starches having approximately two carboxyl groups per monomer unit were as effective as sodium tripolyphosphate on an equal weight basis in the detergent formulation. In a five-day biochemical oxygen demand test these products showed low biodegradability. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Clinoptilolites of western anatolia as detergent builders

The use of clinoptilolites of Western Anatolia in detergents as phosphate substitutes was investigated. The cations present in the clinoptilolite samples were first exchanged with sodium ions. The washing characteristics of detergent mixtures containing surfactants, clinoptilolite, sodium carbonate and sodium sulphate were analysed. The stains of coffee, tea and tomato paste were tested. The washing tests were repeated for different surfactants, i.e. linear alkyl benzene sulphonate, sodium alkyl sulphate and alcohol ethoxylate and for different co-builders, i.e. sodium carbonate and EDTA. In addition, the effects of detergent dose and detergent formulation on washing were investigated. Other factors affecting the degree of soil removal such as shaking time, temperature and water hardness were also studied. The contribution of clinoptilolite to the washability was compared with zeolite A, zeolite X and sodium tripolyphosphate. Increasing the shaking time and temperature improves the degree of cleaning. LAS was the most effective surfactant for use with clinoptilolite. The washing performance of the detergent mixtures used in the present work was found to be comparable with that of commercial detergents at low washing temperatures.     

Constraints on the disposal of detergent manufacturing waste

The needs of the detergent industry in the 1980s will require the management of many new regulatory and environmental concerns. The rules and regulations on waste disposal are changing rapidly and are likely to have an ever increasing impact on manufacturing processes. An understanding of the current constraints in disposal of waste will minimize the cost and future problems in this aspect of detergent manufacture. In a broader sense, the detergent industry needs to be continually aware of the concerns within governmental agencies, to be informed on proposed regulations that address these concerns and to provide input into the regulatory process. The detergent industry needs to help regulatory agencies resolve their concerns in such a way that restrictions and costs are minimized.     

六偏磷酸钠的应用及制备技术

磷酸钠盐是工业磷酸盐中产量最大、消费量最多的磷化工产品,其技术开发与市场发展都比较成熟,主要有正磷酸钠盐、焦磷酸钠盐、聚磷酸钠盐和偏磷酸钠盐。六偏磷酸钠是一种使用广泛的功能性磷酸盐,可应用于洗涤、水处理、食品、选矿、冶金等工业生产中。综述了六偏磷酸钠的应用领域,并详细介绍了六偏磷酸钠的制备方法以及各种方法的优缺点,主要有磷酸二氢钠两步法和五氧化二磷一步法。提出了六偏磷酸钠生产工艺的发展趋势。     

新型无磷洗涤剂助剂——层状结晶硅酸盐

概述了无磷洗涤剂助剂硅酸盐、无定型硅酸盐、晶状硅酸盐,尤其是层状硅酸盐的各种性能,并对4A沸石及其他助剂的市场状况作了阐述,指出4A沸石仍是洗涤剂行业的主要代磷助剂,层状硅酸盐的价格／性能比将是众多厂家的主要关注点。     

无磷助洗剂δ-层状二硅酸钠

分析了现用助洗剂三聚磷酸钠、4A沸石、偏硅酸钠存在的问题及禁磷的重要性,重点论述了δ-层状结晶二硅酸钠用作助洗剂的各种性能及效果,认为δ-层状结晶二硅酸钠是一种良好的无磷助洗剂,它具有其他助洗剂所不具备的优良性能;对δ-层状结晶二硅酸钠的制备工艺作了简要介绍,并作了市场及在国内工业化生产的可性行分析。     

新型无磷洗衣粉配方的研究

由玉米淀粉为原料开发出新型无磷洗涤助剂———玉米淀粉水解氧化物。玉米淀粉水解氧化物含有大量的羧基,对重金属离子如钙、镁离子等有一定的络合能力。以玉米淀粉水解氧化物为主要洗涤助剂,与LAS、AES、AEO9、1631等表面活性剂进行复配,研究了所设计的27种配方的去污能力,并与标准洗衣粉作对比。实验表明:有18种配方其相对标准粉的去污比值P≥1。其中,玉米淀粉水解氧化物∶AES∶AEO9=25∶5∶2和25∶6∶1这两个配方最佳。由此可见,玉米淀粉水解氧化物是一种具有较好发展前途的洗涤助剂,可代替三聚磷酸钠,解决环保问题。     

聚合物在浓缩无磷洗衣粉配方中的应用及其工艺研究

研究了聚合物在浓缩无磷洗衣粉配方中的应用,以及利用现有的高塔喷粉设备进行工艺改造,生产浓缩无磷洗衣粉。同时,研究了此种工艺下的产品质量,对技术改造前后的能耗和产能进行了对比。结果表明,利用高分子聚合物可以有效改善浓缩粉的抗再沉积和抗灰分能力,利用现有的高塔喷粉设备可以有效提升浓缩无磷洗衣粉的产能并提高热能的利用率。     

洗涤剂市场透视

综述了几大衣物洗涤剂和织物护理品生产商继续不断开发新配方产品、超浓缩型产品以及具有更复杂香型的产品，这些产品不断为消费者所接受，并由此促进了相关领域的进一步发展。在这种不断发展的过程中，生产商应注意洗涤剂最基本的性能是清洗。     

液体洗涤剂中表面活性剂的选择及发展趋势

国内洗涤剂产品的结构变化,为液体洗涤剂带来了极大的发展空间;为顺应世界发展趋势,又面临着巨大的挑战。从液体洗涤剂的分类、国内外产品现状、表面活性剂的选择及发展方向等方面进行了阐述。     

Algerian montmorillonite as a builder in a detergent powder

Algerian montmorillonite treated with sodium chloride was used as a substitute for the builders sodium tripolyphosphate (STPP) and sodium sulfate in a detergent powder. The following performance parameters of the substituted composition powder were examined: pH, foaming, cleaning, sequestering, and ion exchange capacities. The latter factors remained the most important ones for effective detergency. Despite anticipated improvement in hard water ion removal, constant detergency results were observed with the treated montmorillonite-containing powder. This level of efficacy does not meet the cost-effectiveness of a standard detergent powder containing STPP.     

Removal of phosphates from aqueous solutions by using bauxite. I: Effect of pH on the adsorption of various phosphates

In this study, the effect of pH on adsorption of various forms of phosphate onto bauxite was investigated. For this purpose, the adsorption and desorption of inorganic (ortho and condensed) and organic phosphate species were studied. It was observed that the adsorption tendency of the various phosphate forms was different and depended on pH. Maximum adsorption efficiencies for all phosphate forms were achieved in slightly acidic conditions (pH 3.2–5.5). The results of adsorption and desorption studies showed that the adsorption of phosphates onto bauxite is based on a ligand exchange mechanism. The adsorption mechanism of inorganic condensed phosphates and organic phosphates is thought to be more complex than that of orthophosphate. It can be stated that the adsorption of organic phosphates is dependent on the functionality, number, and variety of organic groups. The results of experiments carried out with mixed phosphate solutions showed that the adsorption yields of various phosphate forms are dependent on the composition of the solution. The relative adsorptivity of various phosphates was found to be in the general order of hexametaphosphate > pyrophosphate > orthophosphate > tripolyphosphate > adenosine triphosphate > glycerophosphate > glucose‐1‐phosphate. © 2001 Society of Chemical Industry